Process of substitution chlorination



.Fy 7, 1936. w RAMAGE 2,046,411

PROCESS OF SUBSTITUTION CHLORINATION Filed Sept. 17, 1934 INVENTOR Man/v 0.1%1 7/19 BY/QM 4/ 6% ATTORNEY Patented July 7, 1936 PATENT o1=1=.ica

raoonss or suas'rrrn'non CHLORINATION William D. Ramage, Pittsburg, Calit, assignor to Great Western Electra-Chemical Company, a corporation of California Application September 17, 1934, Serial No. 744.3239

22 Claims. (on. 260-161) This invention relates'to the substitution chlorination of organic compoun s, particularly hydrocarbons, although it is of generic character and applicable to the substitution of chlorine iorf 5 hydrogen in organic compounds generally.

The invention relates primarily to the use.oi

hvpochlorous acid or chlorine monoxide as the chlorinating agent. More specifically, it relates to the in situ use of hypochlorous' acid or its an- 30 hydrid. chlorine monoxide, or in other words to' the use-oi nascent hypochlorous acid or chlorine monoxide. The invention deals especially with the means of generation and application of the chicrinating agent, but is not limited to this is phase of the chlorination.

The invention is not concerned with addition chlorination (or chlorination of unsaturated compounds) and has no connection with the numerous patents covering the use of hypochlorous acid 20 in the manufacture of chlorhydrins and similar compounds.

in attempting the manufacture of para-dichlorbenzene, the classical method was used of direct chlorination at an elevated temperature in 25 the presence of a metal chloride catalyst as aluminum or ferric chloride. This was only moderately successful in that a mixture of mono-, di-, and trlchlor benzenes was secured. In addition, the HCl evolved carried off some benzene; to so render the process economically feasible, these must be recovered. To avoid losses, chlorination had to be discontinued short oi complete conversion of the monoto dichlor to avoid the formation of too much trlchlor benzene from the 35 dichlor. In order to avoid these dimculties. an attempt was made to develop a chlorination method not involving the generation oi hydrochloric acid. The findings of a previous investigation on chlorination of nitrobodies, particularly i relating to the manufacture of chlorpicrin from nitromethane (copending application Number 619,354. U. 5. Patent No. 1,996,388) were utilized to this end. I

I have determined that direct substitution 4P5v chlorination of organic compounds can be eiiected advantageously and without iormation'oi E01 by the use of chlorine in the presence of those metal oxides easily reduced by carbon at elevated temperatures and which cxidesare not 50 too alkaline. In this connection I have iound that the process can be carried out in either an aqueous or a substantially anhydrous medium. Thus, I have chlorinated benzene by suspending therein a finely divided metal oxide such as zinc oxide and passing in chlorine gas while vigorously agitating the mixture to keep the oxide in suspension and secure good contact. Adding a diluent, as carbon tetrachloride, increases the efi'ectiveness of the contact.- The chloride formedis very hygroscopic so that the mass remains sub- 5 stantially anhydrous.

Depending upon the relative amounts of benacne and zinc oxide, zinc oxychloride may be formed. At the end of the chlorination, hvdrochloric acid solution may be added to complete the conversion of oxychloride to chloride, and the strong metal chloride solution may then be drawn off from the chlorinated material.

I believe it probable that the effective chlorinating agent is hypochlorous acid or its anhydrid, chlorine monoxide. In the case of aqueous conditions, this reaction can be written:

In either case, the reaction between the nascent hypochlorous acid (or chlorine monoxide) and the material to be chlorinated is so rapid that no considerable concentration of H010 or C120 is present at any one time. The value of hypochlorous acid and chlorine monoxide as substitution chlorination agents has not been recognized previously because of the difllc'ulty of control and the danger of explosion in the case where large preliminary concentrations of 0120 are allowed to be present. Furthermore, the exact control of 1 conditions (e. g. pH) favorable to this type of chlorination has not been determined heretofore, 40

because it has not been realized that exact control of the reaction is possible.

It will be noted that water is formed from the hydrogen which is displaced by chlorine. Under anhydrous conditions, this water is taken up by 4 the metal chloride, but whether or not this is rapid enough to avoid hydrolysis of the anhydrid,

I have not determined. In any case, the chlorinating agent generated is very vigorous and I am able to chlorinate materials'to produce compounds which cannot be secured by chlorination with chlorine alone, nor with Cl: plus catalysts at the temperature used. Under aqueous conditions, the water formed has no effect on the reaction, and hypochlorous acid is probably the active chlorinating agent although I am not sure. In any event,'the operation contemplated is such that water is never present in an amount greater than that which will be taken up due to the hygroscopic nature of the metal chlorides formed. Thus, water present initially (see the second equation) does not increase in volume for part is taken up by the chloride and part by the reaction. As to whether or not this dehydration occurs with a rapidity sufficient to avoid hydrolysis I can not say definitely and it may be that part of the action is due to formation ,of the hydrated chlorine monoxide hypochlorous acid. Most satisfactory operation under aqueous conditions is only obtained when the material to be chlorinated is water soluble or miscible with water.

The metal oxides usedare slightly basic and in aqueous medium the chlorination usually therefore occurs at a pI-I'between 5.0 and 8.0. Below pH 5.0, the reaction is uncertain and hard tocontrol. The process of this invention is thus readily distinguished from that disclosed in Townsend 1,468,220 ,wherein HCl is present.

Under the conditions existing 'in Townsend's scrubber I have found that no chlorination oc-'-' curs of the type claimed herein. The presence of hydrochloric acid automatically prevents the formation ofhypochlorous acid, since hydrolysis of the chlorine is prevented. ,Townsenddeals only with aqueous conditions, and by 'his own statement (page 3, line 7) finds that no further material chlorination of the benzol occurs in the scrubber when aqueous suspensions of zinc oxide are used. The chlorination which does take place is obviously due to the chlorine present, since only monochlorbenzene is formed. Chlorine alone will give this result, while a more vigorous chlorinating agent 'is necessary to obtain the higher chlorinated derivatives.

While chlorine monoxide can be generated by passing chlorine over mercuric oxide, I prefer to use other metal oxides because of their cheapness, equal efficiency, and greater safety. It has not been previously recognized that other oxides than I-lgO act in this manner. The reason for this is, I believe, that the equilibrium concentration of chlorine monoxide obtained from these other ox- .ides in the presence of chlorine is so small that chiorous acid) thus displacing the equilibrium in the desired direction. I prefer to use zinc oxide, a ferric oxide or manganese dioxide. Calcium oxide, magnesium oxide, and other strongly alkaline oxides do not function in the manner described which proves that the action described is not mere absorption of generated HCl. The preferred oxides are very weakly basic and they form unstable'hypochlorites. Compounds other than the oxide can be used, for example, the carbonates. This is not as desirable since CO2 is given off, thus eliminating one of the advantages of theprocess. It can be considered that an element of the invention is in the discovery of functional equivalents for mercuric oxide, materials rendering the process commercially practical.

It should be noted that the metal oxide, as used in' thisprocess, is not a catalyst. It is actually one of the reactants and is always present in at least a stoichiometric proportion. The oxide may, of course, be fed in as the reaction proceeds, so that the excess of oxide present at any time may be relatively slight. Better rsults are generally tion mixture is substantially water free. When monoxide is present at any time.

body while a regulated stream of metal chloride 5 and chlorinated body are withdrawn, the whole body beingactiveiy agitated. The organic body chlorinated is in general kept in the liquid phase during the reaction, particularly when the reacthe oxide is suspended in water or in an inert diluent such as C014, the organic body can be introduced as gas or vapor, if it is soluble in water or in the diluent.

.- The process is also applicable to gas phase reactions. A mixture of methane and chlorine may,

for example, be passed through a tower filled with zinc oxide (or iron oxide). Temperature control may be secured by passing zinc chloride (or ferric chloride) solution down through the tower as the 20 reacting gases pass upward. Fresh oxide is fed in at the top of the tower and the chlorinated derivatives pass oil to a condenser.

It is in general the object of the present-invention to provide an improved substitution chorina- 25 tion process for organic compounds.

Another object is to providea process for the substitution chlorination of organic compounds without generation of hydrochloric acid or other gaseous product.

Another object is to provide a process for the manufacture of dichlorbenzenes, particularly the para.

Afurther object is to provide a process for substitution chlorination with hypochiorous acid or 35 its anydrid produced in direct and immediate contact with the material to be chlorinated.

Another object is to provide a chlorination ,process for substitution chlorination under only moderately alkaline or acid conditions. 40

A further object is to provide for substitution chlorination withfhypochlorous acid or its anhydrid under suchconditions that no dangerous concentration of hypochiorous acid or chlorine 46 Other objects will appear in the following wherein I have outlined certain chlorination substitutions by way of example and not by way of limitation, inasmuch as the invention is applicable to substitution chlorination of organic materials generally.

The single figure in the ,drawing is a diagram of apparatus suitable for application of the-invention in the liquid phase.

In chlorinating, I use an apparatus such as that shown in the drawing. A series of vessels 6, 1 and 8 which can be cooled (usually below C. and about 40 C.), are interconnected by vapor lines 9 having valves I0 therein. Each vessel has agitation means therein as agitator II. A chlorine linelZ, with valves i3, supplies chlorine to a distributor l4 in-each vessel. In operation, two vessels, say 8 and 1, are charged with the material, either anhydrous, with atdiluent, or with water present, and the oxide and the vessels closed. The connecting vapor line is opened and chlorine introduced into vessel 8 while both agitators are operated. The vapor line carries unused chlorine (not hydrochloric acid) over into 70 the next vessel where it reacts; When the charge in vessel Bis chlorinated to the degree desired, vessel 8 is connected to vessel I and its agitator operated, whereupon the chlorine is introduced into vessel 1 after the vapor line to vessel 6 is 75 closed: drawofl i8 permits removal of products. In this way chlorine and vapor losses are prevented while continuous operation is secured. Note that no HCl is given oil and that the chlorine which passesirom one vessel to the next is merely that portion which has bubbled through the reaction mixture without making contact. When the chlorine rate and other conditions are properly controlled, the chlorine reacts-completely in the first reaction vessel. The connection to the second vessel acts merely as a safeguard against unexpected changes in oper= sting conditions, such as a sudden increase in the chlorine rate.

in the case of benzene, the treatment, after chlorination, is as follows:

Alter drawing on the contents of one of the vessels and separating the metal chloride solu= tion, the chlorinated benzene is washed with water and with dilute caustic and is then subjected to fractional distillation, either with or without steam. Sharper cuts are obtained if a high vacuum is not used. Any unconverted benzene or monochlorbenzene is returned to the process. The next higher boiling fraction which contains the mixed dichlor derivatives is further treated as described below. I

The trichlor traction or high boiling residue has no value at the present time. It is not advisable, therefore, to attempt complete conversion of the monochlor to dichlor. lire danger of trichlor formation is, however, somewhat less in this method than in the usual method, and if the chlorination is not carried beyond 80% completion, the amount oi trlchlor corresponds to less than 5% oi the total chlorine.

Recovery and purification oi the paradichlor is efiected as follows. mixed with strong salt solution, chilled to about minus is" C. and the paradichior-benzene filtered out. This is pressed to a solid cake as rapidly as possible and then washed with successive portions of water, starting with water at and gradually warming the wash water to approximately id gr (More efiective washing is secured by repulping the para in the wash water,

but very good results have been obtained without repulping.) This removes the last trace of ortho mother lisuor from the paradichlor. The orthodichlor which passes through the filter with the brine is ready for stccs: after separation of the water. The washings, however, are treated separately because of their relatively high content cf paradichlor. The dichlorbenzene which separates from the wash waters is returned to the next batch, preferably ahead of the distillation, since some trichlor may be present as an impurity. rs this way, the maximum recovery of paradichlor is obtained and the ortho-dichlor sufiers a minimum amount oi contamination with para.

After separating the water, the ortho-dlchlorbenzene is further dried by means of drying agents (e. g., by passing it through a CaCla tower) or by warming for a short time under vacuum. The para is dried in the same manner, being kept above its melting point during the treatment. After drying, the para is allowed to solidify and then broken up and graded. The fines may be sold as such or remelted.

According to another method I proceed as iollows. The dichlor fraction is chilled under agitation until completely crystallized, preferably below minus iii C. The crystal mass is then centrifuged, the temperature being made to rise The dichlor fraction is gradually during this operation by blowing a stream of air through the crystal layer. The liquid which separateslrom the crystals below minus 10 C. is largely ortho dichlorbeiizene. The mother liquor separating at. higher tem- 5 peratures contains sufllcient para so that it must be returned to a subsequent batch, preferably I ahead of the distillation, since some trichlor may be present as an impurity. The final temperature of the air blast is close to the melting point of psradichlorbenzene, and the para thus ob tained is suficiently pure for a coercial product. Removal oi the last traces'oi ortho can be effected by a remelting and recrystallizing operation.

The chlorination process set forth. I have found, gives the largest yield oi paradichlorbensene, local over-chlorination being avoided, particularly if an excess of ortbodichlorbenzene is present initially. When a high yield of paradichlorbenzene is desired, a mixture of benzene and orthodichlorbenzene should be used, a proportion or about three to one being satisfactory when chlorinated with chlorine in the presence oi metal oxide. The dichlor benzenes are not 2 produced when benzene and chlorine are brought into contact even in the presence of water and also even when lime is added, Hcmologues of benzene and derivatives thereof can be used in place of benzene to secure chlorine substituted bodies.

The invention is of a generic character and the. mention of benzene is only by way of example and not by way oi limitation. The invention is applicable to the substitution of chlorine generally and the material treated can be whatever material is desired to be subjected to operation of the process, whether it be an aliphatic or an aromatic compound, and whether the chlorination be di rectly in a straight chain, a branch chain, a side chain, or in a cyclic or a ring compound (whether heterocyclic or carbo-cyclic). The materials subject to the successful use of the process are nu merous and l have successfully chlorinated such different materials as aromatic nitro bodies oi which picric acid is mentionedaliphaticnitro bodice and 05. which nitromethane.nitroethane. et cetera,,are mentioned, as well as other primary, secondary, and tertiary nitroparamnes, organic acids, e. acetic acid. Limitation as to the materials to which the process is applicable is not intended; any material subject to chlorination under conditions of the process can be used.

I claim:

l. Chlorinating a saturated organic compound by substituting chlorine therein by the action of chlorine in the presence of a metal oxide of the class consisting of zinc, ferric, and manganese under substantially anhydrous conditions.

2. A substitution chlorination process comprisinc introducing free chlorine into contact with e. liquid saturated organic compound and a non alkaline metal oxide easily reduced by carbon at an elevated temperature under substantially anhydrous conditions.

A substitution chlorination process comprising introducing free chlorine into contact with s.- liquid saturated organic compound and e. non-slkaline metal oxide easily reduced by carbon at an elevated temperature while agitating the compound and oxide in a substantially non-aqueous lquid.

d. A substitution chlorination process comprising introducing tree chlorine into contact with a substantially anhydrous liquid saturated organic saturated; erratic; liqu d which zcampnses: W l i male: bodies: which; con? spending: in; :th'e organic folf sitmifie riric Mid mg riee chlorine to said I I dueling chlorine: sch st fli orga nieboi sicgap'ablepf; yield; i .lor iitie Substitution producawmgen :con-j I met-marine stream: thi plie ietwje a a reactive metal oxide? :tcrnimg therebyiaichloflne product of i said :miezar oxide: king up ally any water present: 5 2 5 5 i 5 reducing chlcr ine substi-i I icit wales consists estate: metal oxide 0 manganese reruns-8* tunes *prddacs an presucrasrssiagmet ucd;

erebyi :a :chiliorlnie sjazbstihygroscopic cnlermateld oi'ine :s'ubstitmtion :ini a chlorine to a suspension in said liquid of a metal oxide of the class of zinc, iron and manganese thereby forming a hygroscopic metal chloride taking up water formed as a result of chlorine substitution in said liquid. v

12. The process of chlorine substitution which comprises reacting chlorine with a saturated organic compound and in the presence of a metal oxide of the class of zinc, iron and manganese thereby forming a hygroscopic chloride and in the absence of a quantity of water more than sufficient to satisfy the hygroscopicity of said chloride. v

J, 13. A chlorination process comprising substituting chlorine in an organic body by the action of chlorine monoxide generated in direct contact with said body.

14. A chlorination process comprising substituting chlorine irr an organic body by the action Bm t i E amounts :ehlorine: 5 -5 7 1 1 Wi 1 5 ass n23: iron: and manganese; wate 1 amusemam t e p o erti s: f a out in t: t

produce a high yield of para-dichlorbenzene.

21. A chlorination process comprising chlorinating with chlorine in the presence of a metal oxide of the class of zinc, manganese and ferric oxide a mixture of benzene and ortho-dichlorbenzene to produce para-dichlorbenze'ne therein, chilling said mixture to solidify dichlorbenzenes, separating solid dichlorbenzene, raising the temperature of said separated dichlorbenzene to liquefy ortho-dichlorbenzene without liquefying substantially para-dichlorbenzene, and removing said ortho-dichlorbenzene.

22. A chlorination process comprising chlorinating with chlorine in the presence of a metal oxide of the class of zinc, manganese and ferric oxide 2. mixture of benzene and ortho-dichlorbenzene to produce para-dichlorbenzene therein,

para-dichlorbenzene. 

